Plastic optical product and plastic lens for spectacles

ABSTRACT

In a plastic optical product, an optical multilayer film  3  having seven layers is formed on a surface of a plastic substrate  1  directly or with an interlayer  2  interposed therebetween. In the layers of the optical multilayer film  3 , a layer on the plastic substrate  1  side is a low refractive index layer, low refractive index layers and high refractive index layers are alternately disposed. At least the high refractive index layer at the center contains substoichiometric titanium oxide. In a plastic lens for spectacles belonging to such a plastic optical product, the plastic substrate  1  is a plastic lens substrate for spectacles, the interlayer  2  is a hard coat film, and the optical multilayer film  3  is an anti-reflective film.

This application claims the entire benefit of Japanese PatentApplication Number 2010-116625 filed on May 20, 2010 and InternationalPatent Application PCT/JP2011/061308 filed on May 17, 2011, the entiretyof which is incorporated by reference.

BACKGROUND OF INVENTION

1. Technical Field

The present invention relates to a plastic optical product and a plasticlens for spectacles that have an optical multilayer film but areexcellent in heat resistance.

2. Background Art

In order to impart anti-reflection properties and the like to plasticlenses, an anti-reflective film including a metal oxide film is formedon a plastic substrate or on a hard coat film of the substrate. Here,the metal oxide film has a smaller coefficient of thermal expansion thanthose of the plastic substrate and the hard coat film. On this account,when a large amount of heat is applied to a plastic lens, the metaloxide film cannot follow the deformation of the plastic substrate or thehard coat film due to their comparatively large thermal expansion andthis may generate cracks on the anti-reflective film.

In order to improve such characteristics against heat and to impart heatresistance, for example, as disclosed in Japanese Laid-open PatentApplication, Publication No. 2009-128820 (JP2009-128820A), it is knownthat a composite layer including at least two metal oxide layers thatcontain the same metallic element but have different oxygen contentsfrom each other is included in an anti-reflective film.

However, in the invention disclosed in JP2009-128820A, in order toimpart heat resistance while maintaining the anti-reflection properties,the composite layer is disposed away from a substrate side (hard coatingside) (via a common anti-reflective multilayer film structure). As aresult, the common anti-reflective multilayer film structure cannotfollow the deformation due to thermal expansion and the heat resistanceis not much improved. In addition, especially in the case of lens forspectacles and the like, a round lens is not used as it is and isusually edged to have a certain outer shape such as an ellipsoidalshape, and then the edged lenses are inserted in a frame to be used.However, the lens in JP2009-128820A cannot be considered to havesignificantly improved heat resistance after inserted in a frame.

Therefore, an object of the present invention is to provide a plasticoptical product and a plastic lens for spectacles that have an opticalmultilayer film but are excellent in heat resistance.

SUMMARY OF THE INVENTION

In order to achieve the object, an invention according to claim 1 ischaracterized in that an optical multilayer film having seven layers isformed on a surface of a plastic substrate directly or with aninterlayer interposed therebetween, with a layer on the plasticsubstrate side being a low refractive index layer, low refractive indexlayers and high refractive index layers are alternately disposed, and atleast the high refractive index layer at the center containssubstoichiometric titanium oxide.

As an invention according to claim 2, in order to achieve an object ofproviding a product that has a simple structure but is excellent in heatresistance in addition to the object mentioned above, the invention ischaracterized in that the high refractive index layer at the centeralone contains substoichiometric titanium oxide.

As an invention according to claim 3, in order to achieve an object ofmore easy production by containing the same material elements in thehigh refractive index layers in addition to the object mentioned above,the invention is characterized in that each of the high refractive indexlayers is formed of substoichiometric titanium oxide or titaniumdioxide.

In order to achieve the object, an invention according to claim 4 is aplastic lens for spectacles including the plastic optical product of theinvention. The plastic lens for spectacles is characterized in that theplastic substrate is a plastic lens substrate for spectacles, theinterlayer is a hard coat film, and the optical multilayer film is ananti-reflective film.

In the present invention, at least the center layer in the opticalmultilayer film contains substoichiometric titanium oxide. This canimprove the following performance of the optical multilayer film to aplastic substrate when heat is applied, while maintaining goodanti-reflective properties and other properties of the opticalmultilayer film. Therefore, an optical member excellent in heatresistance can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a partial sectional view of a surface of a plastic opticalproduct of the present invention.

DESCRIPTION OF EMBODIMENTS

Exemplary embodiments of the present invention will now be describedwith reference to the drawings as appropriate. The embodiment of thepresent invention is not limited to these examples.

In a plastic optical product of the present invention, as shown in FIG.1, on a surface of a plastic substrate 1, an interlayer 2 and an opticalmultilayer film 3 are stacked in this order. The interlayer 2 may not beprovided and the optical multilayer film 3 may be directly stacked onthe plastic substrate 1, and a water repellent film or the like may befurther formed on the optical multilayer film 3.

Examples of the optical product include spectacle lenses, camera lenses,projector lenses, binocular lenses, telescope lenses, and variousfilters. Examples of the material of the plastic substrate 1 include apolyurethane resin, an episulfide resin, a polycarbonate resin, anacrylic resin, a polyethersulfone resin, a poly(4-methylpentene-1)resin, and a diethylene glycol bis(allyl carbonate) resin.

The interlayer 2 corresponds to, for example, a hard coat film providedon a surface of the plastic substrate 1. The hard coat film is made of,for example, an organosiloxane compound, other organic siliconcompounds, or an acrylic compound. The interlayer 2 may include a primerlayer as an underlayer of the hard coat film. In this case, the primerlayer is formed of, for example, a polyurethane resin, an acrylic resin,a methacrylic resin, or an organosilicon resin.

The optical multilayer film 3 is typically formed by, for example,vacuum deposition or sputtering and is formed by alternately stacking alow refractive index layer and a high refractive index layer eachincluding a metal oxide. The low refractive index layer is formed using,for example, silicon dioxide (SiO₂) and the high refractive index layeris formed using, for example, titanium oxide. Usable examples of the lowrefractive index material and the high refractive index material exceptsubstoichiometric titanium oxide include known materials such as Al₂O₃(dialuminum trioxide), Y₂O₃ (diyttrium trioxide). ZrO₂ (zirconiumdioxide), Ta₂O₅ (tantalum pentoxide), HfO₂ (hafnium dioxide), and Nb₂O₅(niobium pentoxide).

In the optical multilayer film 3, when a layer on the plastic substrate1 or the interlayer 2 is a first layer, the first layer is the lowrefractive index layer, and the second layer is the high refractiveindex layer. The optical multilayer film 3 includes stacked seven layersfrom the first layer to the seventh layer in this manner. Examples ofthe function of the optical multilayer film 3 include an anti-reflectivefilm, a mirror, a half mirror, an ND filter, and a hand-pass filter.

In the optical multilayer film 3, at least the center fourth layercontains insufficiently oxidized titanium oxide (substoichiometrictitanium oxide, TiOx, x <2). In other words, the fourth layer alonecontains TiOx and the second and sixth layers contain titanium dioxide(TiO₂) (Example 1), the second and fourth layers contain TiOx and thesixth layer contains TiO₂ (Example 2), the fourth and sixth layerscontain TiOx and the second layer contains TiO₂ (Example 3), or thesecond, fourth, and sixth layers contain TiOx (Example 4).

TiOx is formed from oxygen in a (slightly) insufficient equivalent withrespect to titanium. For example, a titanium oxide such as trititaniumpentoxide is evaporated while feeding oxygen gas, thereby depositing asubstoichiometric titanium oxide on the plastic substrate 1. During thedeposition, the substoichiometric titanium oxide is formed bycontrolling the feeding condition (for example, feeding amount andpressure during film formation) of the oxygen gas (depending on theamount of titanium oxide used). During the deposition, an inert gas maybe fed together with oxygen gas and the feeding condition of the inertgas may be controlled, thereby controlling the insufficient oxidationamount. During the film formation, in order to improve film quality, ionassistance in which an oxygen ion is introduced in combination whilesatisfying a film formation condition, may be appropriately performed ata predetermined accelerating voltage or a predetermined acceleratingcurrent. Alternatively, another ion such as an argon ion may be used inplace of the oxygen ion. In place of the ion assistance or incombination with the ion assistance, plasma treatment may be performed.

When the optical multilayer film 3 has a five-layer structure or anine-layer structure, the low refractive index layer is disposed at thecenter in the whole layers. When the optical multilayer film 3 has athree-layer structure or an eleven-layer structure, the high refractiveindex layer is disposed at the center. However, the three-layerstructure cannot sufficiently impart various functions such as theanti-reflective function. The nine or more-layer structure requires timeand efforts for the formation of the film, and therefore, such astructure is not practical.

Next, Examples and Comparative Examples of the present invention will bedescribed. However. Examples do not limit the scope of the presentinvention.

<<Overview>>

Examples 1 to 4 were prepared as examples and Comparative Examples 1 to8 were prepared as comparative examples. These are all plastic tensesand are different from each other only in the structure of an opticalmultilayer film. Each optical multilayer film of Comparative Examples 1to 4 included seven layers in total and each optical multilayer film ofComparative Examples 5 to 8 included live layers in total. InComparative Example 1, each high refractive index layer contained TiO₂,in Comparative Example 2, the second high refractive index layer alonecontained TiOx, in Comparative Example 3, the sixth high refractiveindex layer alone contained TiOx, and in Comparative Example 4, thesecond and sixth high refractive index layers alone contained TiOx. InComparative Example 5, all high refractive index layers contained TiO₂,in Comparative Example 6, the second high refractive index layer alonecontained TiOx, in Comparative Example 7, the fourth high refractiveindex layer alone contained TiOx, and in Comparative Example 8, both thesecond and fourth high refractive index layers contained TiOx.

<<Plastic Lens Substrate>>

As each plastic lens substrate of Examples 1 to 4 and ComparativeExamples 1 to 8, a round lens produced as the description below or alens obtained by edging the round lens was used. The round lens wasproduced as follows. With respect to materials in a total amount of 100parts by weight including 50 parts by weight of norbornene diisocyanate,25 parts by weight of pentaerythritol tetrakis(3-mercaptopropionate),and 25 parts by weight ofbis(mercaptomethyl)-3,6,9-trithia-1,11-undecanediol, 0.03 part by weightof dibutyltin dichloride was added as a catalyst to prepare ahomogeneous solution. The solution was poured in a mold for lens and thetemperature was raised from 20° C. to 130° C. over 20 hours, therebycuring the materials to produce a round lens substrate. The plastic lenssubstrate had a refractive index of 1.594 an Abbe number of 42, and alens power of −3.00.

<<Hard Coat Film>>

In Examples 1 to 4 and Comparative Examples 1 to 8, a hard coatingsolution described below (including a base solution and variousadditives) was applied onto the plastic lens substrate by dipping, wasdried in an air stream, and was cured by heating at 120° C. for an hourand a half, thereby thrilling a hard coat film having a film thicknessof 3.0 micrometers (μm).

The base solution in the hard coating solution was prepared as follows.In a total amount of 283 parts by weight, 11 parts by weight oftetraethoxysilane, 76 parts by weight ofγ-glycidoxypropyltrimethoxysilane, and 22 parts by weight ofγ-glycidoxypropylmethyldiethoxysilane were added to 150 parts by weightof methanol. To the mixture on ice with stirring, 24 parts by weight of0.01 normal concentration (N) hydrochloric acid was added dropwise,thereby hydrolyzing the material. The mixture was further stirred at 5°C. for about 24 hours to prepare the base solution.

The hard coating solution was prepared as follows. With respect to 283parts by weight of the base solution, 192 parts by weight of methanoldispersed titania sol (HINEX AB20 manufactured by JGC Catalysts andChemicals Ltd.), 0.60 part by weight of a silicon surfactant (L-7604manufactured by Dow Corning Toray Co., Ltd.) as a leveling agent, 20.02parts by weight of itaconic acid, and 8.33 parts by weight ofdicyandiamide were added, and the whole was further stirred at 5° C. forabout 24 hours, thereby preparing the hard coating solution. The hardcoating solution had a solid content of about 30%.

<<Optical Multilayer Film>>

The plastic lens substrate with the hard coat film was set in a vacuumchamber and each layer was sequentially formed by vacuum deposition(odd-numbered layers: SiO₂, even-numbered layers: titanium oxide). Inparticular, each even-numbered layer was formed as follows. Oxygen gaswas introduced into a vacuum chamber so that the pressure during filmformation reached a pressure determined by whether the oxidation wasinsufficient or not (or by an insufficient degree), and TiO₂ or TiOx wasdeposited using trititanium pentoxide as a deposition material. Thereaction pertaining to the film formation is as shown below.

Ti₃O₅+δO₂→3TiOx

The pressures during film formation of the TiOx layers(substoichiometric titanium oxide layers) of Examples 1 to 4 were 5.5E-3Pascal (Pa), 6.0E-3 Pa, 6.0E-3 Pa, and 6.0E-3 Pa, respectively. Here,each number following “E” is regarded as the exponent of 10 and theexponential FIGURE (digit number) is multiplied by the number followedby “E”. In Examples 1 to 3, the pressure during film formation of eachTiO₂ layer was 1.0E-2 Pa.

In Comparative Examples 2 to 4, the pressure during film formation ofeach TiOx layer was 5.5E-3 Pa, and in Comparative Examples 6 to 8, thepressure during film formation of each TiOx layer was 6.0E-3 Pa. InComparative Examples 1 to 7, the pressure during film formation of eachTiO₂ layer was 1.0E-2 Pa.

Each film structure of Examples 1 to 4 is shown in [Table 1], each filmstructure of Comparative Examples 1 to 4 is shown in [Table 2], and eachfilm structure of Comparative Examples 5 to 8 is shown in [Table 3]. In[Table I] to [Table 3], the substoichiometric titanium oxide is shown by“TiOx, insufficient oxidation”.

TABLE 1 AR film Physical film structure thickness [nm] Example 1 Example2 Example 3 Example 4 1st layer 25.91 SiO2 SiO2 SiO2 SiO2 2nd layer13.28 TiO2 TiOx insufficient TiO2 TiOx insufficient oxidation oxidation3rd layer 38.07 SiO2 SiO2 SiO2 SiO2 4th layer 41.50 TiOx insufficientTiOx insufficient TiOx insufficient TiOx insufficient oxidationoxidation oxidation oxidation 5th layer 19.83 SiO2 SiO2 SiO2 SiO2 6thlayer 36.96 TiO2 TiO2 TiOx insufficient TiOx insufficient oxidationoxidation 7th layer 96.31 SiO2 SiO2 SiO2 SiO2 Air side — — — —

TABLE 2 AR film Physical film Comparative Comparative ComparativeComparative structure thickness [nm] Example 1 Example 2 Example 3Example 4 1st layer 25.91 SiO2 SiO2 SiO2 SiO2 2nd layer 13.28 TiO2 TiOxinsufficient TiO2 TiOx insufficient oxidation oxidation 3rd layer 38.07SiO2 SiO2 SiO2 SiO2 4th layer 41.50 TiO2 TiO2 TiO2 TiO2 5th layer 19.83SiO2 SiO2 SiO2 SiO2 6th layer 36.96 TiO2 TiO2 TiOx insufficient TiOxinsufficient oxidation oxidation 7th layer 96.31 SiO2 SiO2 SiO2 SiO2 Airside — — — —

TABLE 3 AR film Physical film Comparative Comparative ComparativeComparative structure thickness [nm] Example 5 Example 6 Example 7Example 8 1st layer 35.22 SiO2 SiO2 SiO2 SiO2 2nd layer 12.71 TiO2 TiOxinsufficient TiO2 TiOx insufficient oxidation oxidation 3rd layer 35.41SiO2 SiO2 SiO2 SiO2 4th layer 112.00 TiO2 TiO2 TiOx insufficient TiOxinsufficient oxidation oxidation 5th layer 84.57 SiO2 SiO2 SiO2 SiO2 Airside — — — —

<<Heat Resistance of Round Lens>>

A round lens after anti-reflective film formation was placed in an ovenat 60° C. for 5 minutes, and then was taken out. The presence or absenceof abnormal changes such as cracks was observed in the appearance. Whenno appearance defect was observed, the lens was placed in an oven in asimilar manner once again and the appearance was observed. Thisoperation was repeated until the total oven treatment time reached 30minutes. When no appearance defect was observed even after that, thetemperature of the oven was raised by 10° C., and heating every 5minutes and the appearance observation were repeated until the totaloven treatment time reached 30 minutes in a similar manner. Thisprocedure was repeated until the appearance defect was observed. Eachtest result of Examples 1 to 4 is shown in upper lines in [Table 4],each test result of Comparative Examples 1 to 4 is shown in upper linesin [Table 5], and each test result of Comparative Examples 5 to 8 isshown in upper lines in [Table 6]. These results reveal that each roundlens could be resistant to heat at 120° C.

TABLE 4 Example 1 Example 2 Example 3 Example 4 4th layer, 2nd and 4thlayers, 4th and 6th layers, 2nd, 4th, and 6th layers, substoichiometricsubstoichiometric substoichiometric substoichiometric titanium oxidelayer titanium oxide layer titanium oxide layer titanium oxide layerRound lens  60° C. ◯ ◯ ◯ ◯ heat  70° C. ◯ ◯ ◯ ◯ resistance  80° C. ◯ ◯ ◯◯  90° C. ◯ ◯ ◯ ◯ 100° C. ◯ ◯ ◯ ◯ 110° C. ◯ ◯ ◯ ◯ 120° C. ◯ ◯ ◯ ◯ 130°C. X X X X Acceleration Initial state of ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ heatacceleration resistance  60° C. ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ of frame  70° C. ◯ ◯ ◯ ◯◯ ◯ ◯ ◯ (two lenses)  80° C. ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯  90° C. ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ 95° C. ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ 100° C. ◯ ◯ ◯ X ◯ ◯ X ◯ 105° C. ◯ ◯ ◯ — ◯ X — ◯110° C. X X X — ◯ — — X 115° C. — — — — X — — — Average heat resistance105° C. 100° C. 105° C. 100° C. temperature of two lenses

TABLE 5 Comparative Example 1 Comparative Example 2 Comparative Example3 Comparative Example 4 Without 2nd layer, 6th layer, 2nd and 6thlayers, substoichiometric substoichiometric substoichiometricsubstoichiometric titanium oxide layer titanium oxide layer titaniumoxide layer titanium oxide layer Round lens  60° C. ◯ ◯ ◯ ◯ heat  70° C.◯ ◯ ◯ ◯ resistance  80° C. ◯ ◯ ◯ ◯  90° C. ◯ ◯ ◯ ◯ 100° C. ◯ ◯ ◯ ◯ 110°C. ◯ ◯ ◯ ◯ 120° C. ◯ ◯ ◯ ◯ 130° C. X X X X Acceleration Initial state of◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ heat acceleration resistance  60° C. ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ offrame  70° C. ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ (two lenses)  80° C. X X X X ◯ ◯ ◯ ◯  90°C. — — — — X X X X  95° C. — — — — — — — — 100° C. — — — — — — — — 105°C. — — — — — — — — 110° C. — — — — — — — — 115° C. — — — — — — — —Average heat resistance 70° C. 70° C. 80° C. 80° C. temperature of twolenses

TABLE 6 Comparative Example 5 Comparative Example 6 Comparative Example7 Comparative Example 8 Without 2nd layer, 4th layer, 2nd and 4thlayers, substoichiometric substoichiometric substoichiometricsubstoichiometric titanium oxide layer titanium oxide layer titaniumoxide layer titanium oxide layer Round lens  60° C. ◯ ◯ ◯ ◯ heat  70° C.◯ ◯ ◯ ◯ resistance  80° C. ◯ ◯ ◯ ◯  90° C. ◯ ◯ ◯ ◯ 100° C. ◯ ◯ ◯ ◯ 110°C. ◯ ◯ ◯ ◯ 120° C. ◯ ◯ ◯ ◯ 130° C. X X X X Acceleration Initial state of◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ heat acceleration resistance  60° C. ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ offrame  70° C. ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ (two lenses)  80° C. ◯ ◯ X X ◯ ◯ X ◯  90°C. ◯ ◯ — — ◯ ◯ — ◯  95° C. ◯ X — — ◯ ◯ — ◯ 100° C. X — — — ◯ X — X 105°C. — — — — X — — — 110° C. — — — — — — — — 115° C. — — — — — — — —Average heat resistance 92.5° C. 70° C. 97.5° C. 82.5° C. temperature oftwo lenses

<<Heat Resistance in Frame>>

Two plastic lenses that were obtained by edging round lenses wereinserted into left and right positions of a metal spectacle frame. Theframe was placed in a constant temperature and humidity environment at60° C. and 95% for three days, and the same heat resistance test wasperformed as the test for round lenses. However, the heating time ateach temperature was 20 minutes. When no appearance defect was observed,the frame was immediately heated at a next higher temperature. In theheating at 90° C. or more, the temperature was raised by 5° C. When anappearance defect was observed in one of the left and right lenses butno appearance defect was observed in the other, the test was continued.When lenses in a frame is placed in the constant temperature andhumidity environment for three days, the state after the lenses are usedfor a long period of time can be achieved in a short period of time.This enables the acceleration of test of heat resistance considering theuse. Each test result of Examples 1 to 4 is shown in lower lines in[Table 4], each test result of Comparative Examples 1 to 4 is shown inlower lines in [Table 5], and each test result of Comparative Examples 5to 8 is shown in upper lines in [Table 6]. In the lower lines in [Table4] and others, the result of each left lens was shown in a correspondingleft column and the result of each right lens was shown in acorresponding right column.

From the results, Comparative Example 1 in which TiOx was not used in aseven-layer structure was resistant to heat at a low temperature of 70°C. and Comparative Examples 2 to 4 in which TiOx was used in a layerexcept the center layer was resistant to heat at a low temperature of 70to 80° C. Comparative Examples 1 to 4 having a five-layer structure wereresistant to heat at a low temperature of 70 to 97.5° C. (average ofleft and right) regardless of whether TiOx was used or not. In contrast,Examples 1 to 4 were resistant to heat at 100 to 105° C. and, inparticular, in Example 1 in which the center layer alone contained TiOx,both left and right lenses were resistant to heat at 105° C. and wereexcellent in heat resistance and balance of the lenses.

<<Weather Resistant Adhesiveness>>

On an optical multilayer film surface on a round lens, 100 squarecompartments having an area of 1 square millimeter (mm²) were formedusing a knife. Then, a piece of long adhesive tape was attached so as tocover all the compartments. One end of the tape that was not attached tothe lens was held and the tape was peeled at once in a directionperpendicular to the lens surface. After peeling the tape, the number ofremaining compartments of the optical multilayer film was counted byappearance (a compartment, from which an optical multilayer film isremoved, leaves a trace of peeled coating). This peeling test (adherenceevaluation test) was carried out once again after a lens was placed in asunshine weather meter that mimicked sunshine for 60 hours. The peelingtest was repeated every 60 hours of the sunshine application until thetotal sunshine treatment time reached 240 hours. Each test result ofExamples 1 to 4 is shown in upper lines in [Table 7], each test resultof Comparative Examples 1 to 4 is shown in upper lines in [Table 8], andeach test result of Comparative Examples 5 to 8 is shown in upper linesin [Table 9]. Here, “⊚” represents that the number of remainingcompartments was 100 to 99. These results reveal that each lens hadexcellent weather resistant adhesiveness and Examples 1 to 4 had weatherresistant adhesiveness equivalent to those of Comparative Examples 1 to8 (especially Comparative Examples 1 and 5 without TiOx),

TABLE 7 Example 1 Example 2 Example 3 Example 4 4th layer, 2nd and 4thlayers, 4th and 6th layers, 2nd, 4th, and 6th layers, substoichiometricsubstoichiometric substoichiometric substoichiometric titanitun oxidelayer titanium oxide layer titanium oxide layer titanium oxide layerWeather  0 hr ⊚ ⊚ ⊚ ⊚ resistant  60 hr ⊚ ⊚ ⊚ ⊚ adhesiveness 120 hr ⊚ ⊚ ⊚⊚ (convex face/ 180 hr ⊚ ⊚ ⊚ ⊚ concave face) 240 hr ⊚ ⊚ ⊚ ⊚ ArtificialAcid ◯ ◯ ◯ ◯ sweat Alkali ◯ ◯ ◯ ◯ Boiling Pure water ◯ ◯ ◯ ◯ Tap water ◯◯ ◯ ◯

TABLE 8 Comparative Example 1 Comparative Example 2 Comparative Example3 Comparative Example 4 Without 2nd layer, 6th layer, 2nd and 6thlayers, substoichiometric substoichiometric substoichiometricsubstoichiometric titanium oxide layer titanium oxide layer titaniumoxide layer titanium oxide layer Weather  0 hr ⊚ ⊚ ⊚ ⊚ resistant  60 hr⊚ ⊚ ⊚ ⊚ adhesiveness 120 hr ⊚ ⊚ ⊚ ⊚ (convex face/ 180 hr ⊚ ⊚ ⊚ ⊚ concaveface) 240 hr ⊚ ⊚ ⊚ ⊚ Artificial Acid ◯ ◯ ◯ ◯ sweat Alkali ◯ ◯ ◯ ◯Boiling Pure water ◯ ◯ ◯ ◯ Tap water ◯ ◯ ◯ ◯

TABLE 9 Comparative Example 5 Comparative Example 6 Comparative Example7 Comparative Example 8 Without 2nd layer, 4th layer, 2nd and 4thlayers, substoichiometric substoichiometric substoichiometricsubstoichiometric titanium oxide layer titanium oxide layer titaniumoxide layer titanium oxide layer Weather  0 hr ⊚ ⊚ ⊚ ⊚ resistant  60 hr⊚ ⊚ ⊚ ⊚ adhesiveness 120 hr ⊚ ⊚ ⊚ ⊚ (convex face/ 180 hr ⊚ ⊚ ⊚ ⊚ concaveface) 240 hr ⊚ ⊚ ⊚ ⊚ Artificial Acid ◯ ◯ ◯ ◯ sweat Alkali ◯ ◯ ◯ ◯Boiling Pure water ◯ ◯ ◯ ◯ Tap water ◯ ◯ ◯ ◯

<<Resistance to Sweat>>

A round lens was immersed in each of an acidic artificial sweat liquidand an alkaline artificial sweat liquid for 24 hours and the state ofthe optical multilayer film was observed. The acidic artificial sweatliquid was prepared by dissolving 10 grams (g) of sodium chloride, 2.5 gof sodium hydrogen phosphate dodecahydrate, and 1.0 g of lactic acid in1 liter of pure water. The alkaline artificial sweat liquid was preparedby dissolving 10 g of sodium chloride, 2.5 g of sodium hydrogenphosphate dodecahydrate, and 4.0 g of ammonium carbonate in 1 liter ofpure water. Each test result of resistance to sweat of Examples 1 to 4is shown in middle lines in [Table 7], each result of ComparativeExamples 1 to 4 is shown in middle lines in [Table 8], and each resultof Comparative Examples 5 to 8 is shown in middle lines in [Table 9].Here, “◯” represents that an optical multilayer film was not peeled. Theresults revealed that each lens had excellent resistance to sweat.

<<Boiling Resistance>>

A round lens was immersed in boiling tap water or boiling pure water for10 minutes, and then was taken out. The lens surface was observed. Eachtest result of Examples 1 to 4 is shown in lower lines in [Table 7],each test result of Comparative Examples 1 to 4 is shown in lower linesin [Table 8], and each test result of Comparative Examples 5 to 8 isshown in lower lines in [Table 9], in the same manner as in the case ofthe resistance to sweat. The results reveal that each lens had excellentboiling resistance.

<<Others>>

Even when Al₂O₃, Y₂O₃, ZrO₂, Ta₂O₅, HfO₂, or Nb₂O₅ was used as the lowrefractive index material or the high refractive index material exceptthe substoichiometric titanium oxide, the obtained lens had heatresistance and the like in the same manner as in the case where SiO₂ andTiO₂ were used.

CONCLUSION

As described above, by the arrangement of a TiOx layer in at least thecenter layer of a seven-layer structure, a lens maintains good adhesionproperties, resistance to sweat, and boiling resistance equivalent tothose of a lens that includes a TiO₂ layer alone as the high refractiveindex material and a lens that includes a TiOx layer in addition to thecenter layer. At the same time, the lens has uniformly controlled stressbalance in the entire film area and good following performance to stresschange of a substrate or an interlayer, and can suppress appearancedefects such as cracks for a long period of time even after the lens isedged or is inserted into a frame.

1. A plastic optical product comprising: a plastic substrate; and anoptical multilayer film having seven layers and formed on surface of theplastic substrate directly or with an interlayer interposedtherebetween, wherein with a layer on the plastic substrate side being alow refractive index layer, low refractive index layers and highrefractive index layers are alternately disposed, and at least the highrefractive index layer at center contains substoichiometric titaniumoxide.
 2. The plastic optical product according to claim 1, wherein thehigh refractive index layer at the center alone containssubstoichiometric titanium oxide.
 3. The plastic optical productaccording to claim 1, wherein each of the high refractive index layersis formed of substoichiometric titanium oxide or titanium dioxide. 4.The plastic optical product according to claim 2, wherein each of thehigh refractive index layers is formed of substoichiometric titaniumoxide or titanium dioxide.
 5. A plastic lens for spectacles comprising:the plastic optical product according to claim 1, wherein the plasticsubstrate is a plastic lens substrate for spectacles, the interlayer isa hard coat film, and the optical multilayer film is an anti-reflectivefilm.
 6. A plastic lens for spectacles comprising: the plastic opticalproduct according to claim 2, wherein the plastic substrate is a plasticlens substrate for spectacles, the interlayer is a hard coat film, andthe optical multilayer film is an anti-reflective film.
 7. A plasticlens for spectacles comprising: the plastic optical product according toclaim 3, wherein the plastic substrate is a plastic lens substrate forspectacles, the interlayer is a hard coat film, and the opticalmultilayer film is an anti-reflective film.
 8. A plastic lens forspectacles comprising: the plastic optical product according to claim 4,wherein the plastic substrate is a plastic lens substrate forspectacles, the interlayer is a hard coat film, and the opticalmultilayer film is an anti-reflective film.